U.S. patent number 4,791,084 [Application Number 07/058,979] was granted by the patent office on 1988-12-13 for hydrocarbon catalytic cracking catalyst compositions and method therefor.
This patent grant is currently assigned to Catalysts & Chemicals Industries Co., Ltd.. Invention is credited to Takanori Ida, Tatsuo Masuda, Masamitsu Ogata, Goro Sato.
United States Patent |
4,791,084 |
Sato , et al. |
December 13, 1988 |
Hydrocarbon catalytic cracking catalyst compositions and method
therefor
Abstract
A cracking catalyst for hydrocarbons with superior selectivity
to gasoline production and greater metals tolerance comprising a
porous inorganic oxide matrix composited with a crystalline
aluminosilicate zeolite and a phosphorus-containing alumina in the
form of small lumps.
Inventors: |
Sato; Goro (Kitakyushu,
JP), Ogata; Masamitsu (Kitakyushu, JP),
Ida; Takanori (Kitakyushu, JP), Masuda; Tatsuo
(Kitakyushu, JP) |
Assignee: |
Catalysts & Chemicals
Industries Co., Ltd. (Tokyo, JP)
|
Family
ID: |
27335895 |
Appl.
No.: |
07/058,979 |
Filed: |
June 8, 1987 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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808414 |
Dec 12, 1985 |
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Foreign Application Priority Data
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Dec 21, 1984 [JP] |
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59-271199 |
Dec 21, 1984 [JP] |
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59-271200 |
Dec 21, 1984 [JP] |
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59-271201 |
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Current U.S.
Class: |
502/65;
502/64 |
Current CPC
Class: |
B01J
29/06 (20130101); C10G 11/05 (20130101) |
Current International
Class: |
B01J
29/06 (20060101); B01J 29/00 (20060101); C10G
11/00 (20060101); C10G 11/05 (20060101); B01J
029/06 (); B01J 027/18 () |
Field of
Search: |
;502/64,214,65
;208/114 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Dees; Carl F.
Attorney, Agent or Firm: Flynn, Thiel, Boutell &
Tanis
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of Ser. No. 808 414,
filed Dec. 12, 1985.
Claims
We claim:
1. A catalyst composition for the catalytic cracking of
hydrocarbons, which comprises:
a porous inorganic oxide matrix containing mixed therein (1)
particles of crystalline aluminosilicate zeolite and (2) alumina
particles having a particle diameter of from 15 to 60 .mu.m and
impregnated with a phosphorus component.
2. A catalyst composition according to claim 1, wherein said
alumina particles have a P/Al atomic ratio in the range of
0.01-0.20.
3. A catalyst composition according to claim 1, consisting
essentially of from 5 to 75 wt. % of said alumina particles, from 5
to 50 wt. % of said crystalline aluminosilicate zeolite particles
and from 20 to 50 wt. % of said porous inorganic oxide matrix.
4. A catalyst composition according to claim 1, which has been
prepared by contacting alumina or alumina hydrate particles with a
solution of a phosphorus compound having a phosphoric ion to
impregnate said alumina particles with said phosphorus compound,
then calcining said alumina particles at from 250.degree. to
850.degree. C., then mixing said alumina particles with said
zeolite particles and with an aqueous slurry containing a precursor
of said porous inorganic oxide matrix, and then drying said slurry
to obtain said catalyst composition.
5. A catalyst composition according to claim 1, in which said
porous inorganic oxide matrix is selected from the group consisting
of silica, silica-alumina and silica-magnesia. magnesia.
6. A catalyst composition for the catalytic cracking of
hydrocarbons, which comprises:
a porous inorganic oxide matrix containing mixed therein (1)
particles of crystalline aluminosilicate zeolite and (2) alumina
particles having a particle diameter of from 15 to 60 .mu.m and
impregnated with (a) a phosphorus component and (b) at least one
auxiliary component selected from the group consisting of alkaline
earth metals, rare earth metals, antimony, bismuth, boron,
manganese and tin.
7. A catalyst composition according to claim 6, wherein said
auxiliary component is selected from the group consisting of
alkaline earth metals and rare earth metals, and the amount of said
auxiliary component deposited on the alumina particles is in the
range of 0.1-5 wt. % of the alumina particles.
8. A catalyst composition according to claim 6, wherein the
auxiliary component is selected from the group consisting of
antimony, bismuth, boron, manganese and tin, and the amount of the
auxiliary component deposited on the alumina particles is in the
range of 0.001-5 wt. % of the alumina particles.
9. A catalyst composition according to claim 6, wherein said
alumina particles have a P/Al atomic ratio in the range of
0.01-0.20.
10. A catalyst composition according to claim 6, consisting
essentially of from 5 to 75 wt. % of said alumina particles, from 5
to 50 wt. % of said crystalline aluminosilicate zeolite particles
and from 20 to 50 wt. % of said porous inorganic oxide matrix.
11. A catalyst composition according to claim 6, which has been
prepared by contacting alumina or alumina hydrate particles with a
solution of a phosphorus compound having a phosphoric ion and the
same or a different solution containing a compound of said
auxiliary component to impregnate said alumina particles with said
compounds, then calcining said alumina particles at from
250.degree. to 850.degree. C., then mixing said alumina particles
with said zeolite particles and with an aqueous slurry containing
precursor of said porous inorganic oxide matrix, and then drying
said slurry to obtain said catalyst composition.
12. A catalyst composition according to claim 6, in which said
porous inorganic oxide matrix is selected from the group consisting
of silica, silica-alumina and silica-magnesia.
13. A method for preparing a catalyst composition for the catalytic
cracking of hydrocarbons, which comprises the steps of mixing (a)
alumina particles having a particle diameter of from 15 to 60 .mu.m
and impregnated with a phosphorus compound, with (b) particles of
crystalline aluminosilicate zeolite and with (c) an aqueous slurry
of a precursor of a porous inorganic oxide matrix to form a
catalyst slurry; and then spray-drying the catalyst slurry.
14. A method for preparing a catalyst composition for the catalytic
cracking of hydrocarbons, which comprises the steps of mixing (a)
alumina particles having a particle diameter of from 15 to 60 .mu.m
and impregnated with a phosphorus compound and with at least one
auxiliary component selected from the group consisting of alkaline
earth metals, rare earth metals, antimony, bismuth, boron,
manganese and tin, with (b) particles of crystalline
aluminosilicate zeolite and with (c) an aqueous slurry of a
precursor of a porous inorganic oxide matrix to form a catalyst
slurry; and then spray drying the catalyst slurry.
Description
BACKGROUND OF THE INVENTION
The present invention relates to hydrocarbon catalytic cracking
catalyst compositions and in particular relates to catalyst
compositions which exhibit high metal tolerance, maintain high
catalytic activity and gasoline selectivity for a long period of
time and can depress hydrogen and coke formation to a low level
when used in catalytic cracking of heavy oil containing large
amounts of heavy metals such as vanadium, nickel, iron, copper and
the like and a method therefor.
Catalytic cracking of hydrocarbon originally aims at the production
of gasoline. Therefore, catalysts used therefor are naturally
demanded to exhibit high catalytic activity and gasoline
selectivity, and further, metal tolerance.
In recent years, it is becoming necessary, with deterioration of
the oil situation, to employ low grade heavy oils, typically
residual oils, containing large amounts of heavy metals such as
vanadium, nickel, iron, copper and the like as a feed stock for
catalytic cracking. This attaches more importance to metal
tolerance of catalytic cracking catalysts.
In catalytic cracking of heavy oils, the cracking activity and
gasoline selectivity of the catalyst used therefor generally
deteriorate more or less because of the deposit of metallic
contaminants contained in feed oils on the catalyst. In view of
this, it is customary that the usual commercially used catalytic
cracking catalysts, exemplarily catalytic cracking catalysts
comprising zeolite dispersed in porous inorganic oxide matrices,
have such metal tolerance that they can maintain a satisfactory
catalytic ability even when a certain degree of metals deposit
thereon. However, in catalytic cracking of the above mentioned low
grade heavy oils using the catalyst of this sort, it is impossible
to achieve the primary object of catalytic cracking because a large
amount of metallic contaminants admixed with said oils deposit on
the catalyst whereby a dehydrogenation reaction is accelerated,
formation of hydrogen and coke is increased, and further, the
crystal structure of zeolite is apt to be destroyed.
Accordingly, when subjecting the low grade heavy oils containing a
large amount of metallic contaminants to catalytic cracking, there
have usually been employed the procedure of suppressing the
deposited amount of metal per catalyst particle by increasing the
amount of catalyst used, the procedure of preventing the
deterioration of the catalytic activity caused by metal deposit by
adding an antimony compound in the feed oil, or the like. However,
these operational countermeasures can never be recommended because
the running cost increases. On the other hand, as the
countermeasure from the catalytic ability there has been known the
one which comprises increasing the amount of zeolite to be
dispersed in the catalyst in comparison with that in the normal
catalytic cracking catalyst, and further, U.S. Pat. No. 4,430,199
discloses a catalytic cracking catalyst improved in metals
tolerance by incorporating a phosphorus compound in a
zeolite-containing catalytic cracking catalyst. Still further, U.S.
Pat. No. 4,228,036 discloses a catalytic cracking catalyst prepared
by dispersing zeolite in a matrix comprising alumina-aluminum
phosphate-silica.
In addition, U.S. Pat. No. 3,711,422 describes that the addition of
an antimony compound to a catalytic cracking catalyst deactivates
the metallic contaminants deposited on said catalyst, and U.S. Pat.
No. 4,183,803 describes a process for passivating metallic
contaminants by contacting the metallic contaminants-deposited
catalyst with a compound of antimony, bismuth, phosphorus or the
like.
In addition, U.S. Pat. No. 4,222,896 proposes a catalyst comprising
a MgO-Al.sub.2 O.sub.3 -AlPO.sub.4 matrix composited with zeolite,
and Japanese Laid Open Patent Application 150539/1984 proposes a
catalyst comprising an alumina-magnesia matrix composited with
zeolite, respectively. Of the usual catalytic cracking catalysts
developed in order to improve metals tolerance thereof, the
catalyst whose zeolite content has been increased can never be made
a commercially attractive one. The catalyst containing a phosphorus
component with or without antimony, bismuth, magnesium and the like
is not necessarily satisfactory in metal tolerance. The phosphorus
component and the above mentioned other metals are surely
attributable to improvement in metals tolerance, but it is
conjectured that the usual catalysts, wherein the phosphorus
component and other metallic components are dispersed uniformly
throughout the catalysts, can never obtain satisfactory results
when too much metal deposits thereon because the metal tolerance of
the catalysts deteriorates.
We have found that when an alumina-containing catalytic cracking
catalyst is utilized for catalytic cracking of hydrocarbon oils and
vanadium is deposited thereon, and when the spent catalyst is
analyzed by means of an X-ray microanalyzer, the distribution of
the deposited vanadium well corresponds to that of alumina. This
fact suggests that when alumina is allowed to be present, taking
the form of small particles or lumps, in the catalytic cracking
catalyst, metallic contaminants can be deposited preferentially on
these small particles or lumps of alumina.
SUMMARY OF THE INVENTION
The present invention provides a hydrocarbon catalytic cracking
catalyst composition that comprises alumina particles having a
particle diameter of 2-60 .mu.m, particularly 10-60 .mu.m, on which
a phosphorus component has previously been fixed, with or without
one or more kinds of auxiliary components selected from the group
consisting of alkaline earth metals, rare earth metals, antimony,
bismuth, boron, manganese and tin, a crystalline aluminosilicate
zeolite and a porous inorganic oxide matrix. A more preferable
particle diameter range for the alumina particles is from 15-60
.mu.m and the most preferred diameter range is from 20-60 .mu.m.
Further, the present invention provides a method for preparing said
catalyst compositions, and said method comprises spray drying an
alumina particle on which a phosphorus component has previously
been fixed, with or without an auxiliary component, a crystalline
aluminosilicate zeolite and an aqueous slurry containing a
precursor of a matrix. In the catalyst composition according to the
present invention, the amount of said alumina particles on which a
phosphorus component has previously been fixed, with or without an
auxiliary component, may be controlled in the range of 5-75 wt. %
of the catalyst composition, the amount of said aluminosilicate
zeolite may be controlled in the range of 5-50 wt. % of the
catalyst composition, and the amount of said porous inorganic oxide
matrix may be controlled in the range of 20-50 wt. % of the
catalyst composition, re- spectively.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graph obtained by analyzing Catalyst A, prepared in
Example 1 referred to afterwards and used in Example 2, by means of
an x-ray microanalyzer.
FIG. 2 is a graph obtained by analyzing Catalyst B, prepared in
Comparative Example 1 and used in Example 2, by means of an X-ray
microanalyzer.
FIG. 3 as a graph plotting the conversion of the feed oil, using
nickel and vanadium-deposited catalysts, against the diameters of
phosphorus-containing alumina particles of said catalysts.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The alumina particle on which the phosphorus component is fixed,
with or without the auxiliary component, must have a particle
diameter in the range of 2-60 .mu.m, preferably 10-60 .mu.m. The
reason is that when using a fine alumina particle whose particle
diameter is smaller than this range, said alumina particle
disperses uniformly in the catalyst composition without existing
therein in the form of small lumps of alumina, while a particle
diameter larger than said range is not preferable in connection
with the average particle diameter of the finally obtained catalyst
composition.
In view of this, the alumina particles of the present invention on
which the phosphorus component has been fixed are prepared by the
method of contacting a previously prepared alumina or alumina
hydrate having a particle diameter of 2-60 .mu.m, preferably 10-60
.mu.m, with a phosphoric ion (PO.sub.4.sup.3-)-containing aqueous
solution, drying and thereafter calcining the alumina particles, or
by the method of contacting a coarse alumina particle or alumina
hydrate with a phosphoric ion-containing aqueous solution, drying,
calcining and thereafter pulverizing the same into a particle
diameter of 2-60 .mu.m, preferably 10-60 .mu.m. When impregnating
the alumina particle with the auxiliary component of the present
invention together with the phosphorus component, it is possible to
impregnate both components simultaneously using a mixed solution of
a phosphoric ion-containing aqueous solution and an auxiliary
component-containing aqueous solution, and it is also possible to
impregnate both components separately. In the latter case, the
order of impregnation does not matter, but it is preferable to dry
the alumina and calcine it once after the first impregnation has
been completed. In any case, as said phosphoric ion-containing
aqueous solution, there can be used aqueous solutions of phosphoric
acid, ammonium hydrogen phosphate, ammonium phosphate, ester
phosphates or the like or their mixed solutions. As the auxiliary
component-containing aqueous solution, there may be used, singly or
in admixture, an aqueous solution of nitrate, carbonate, chloride
or the like containing one or two kinds or more of alkaline earth
metals, rare earth metals, antimony, bismuth, manganese and tin and
an aqueous solution of boric acid.
The amount of the phosphorus introduced in the alumina particle
having a particle diameter of 10-60 .mu.m preferably is in the
range of 0.6-12.2 wt. % (P/Al atomic ratio 0.01-0.20) based on
alumina and calculated as elementary phosphorus, because in case
said amount is less than this range, there is not displayed any
effect resulting from the introduction of phosphorus, while in case
said amount is more than this range, the pore volume of the alumina
decreases too much. On the other hand, when the auxiliary component
of the present invention is selected from alkaline earth metals and
rare earth metals, the preferable amount of said auxiliary
component introduced is in the range of 0.1-5 wt. % based on
alumina and calculated as elementary metal.
In case said amount deviates from this range, expected results can
never be obtained. When the auxiliary component of the present
invention is selected from antimony, bismuth, boron, manganese and
tin, the preferable amount of said auxiliary component introduced
is in the range of 0.001-5 wt. % based on alumina amd calculated as
elementary metal. In case said amount deviates from this range,
expected results can never be obtained. The alumina particle in
which the phosphorus has been introduced, with or without the
auxiliary component, is then calcined at a temperature in the range
of 250.degree.-850.degree. C. whereby the phosphorus component is
fixed on the alumina particle, with or without the auxiliary
component.
The crystalline aluminosilicate zeolite according to the present
invention includes a synthetic Y-type zeolite, mordenite, a ZSM
type zeolite, a natural zeolite and the like. These are used, as in
the case of normal catalytic cracking catalysts, in the form
ion-exchanged by the cation selected from hydrogen, ammonium and
polyvalent metals. As the porous inorganic oxide, there may be used
silica, silica-alumina, silica-magnesia and the like, and further
there may be used also in the present invention a matrix component
used usually in normal catalytic cracking catalysts.
The catalyst composition of the present invention may be prepared
in the same manner as the method for preparing a usual crystalline
aluminosilicate zeolite catalytic cracking catalyst except for
using the above mentioned specific alumina particle. That is, the
catalyst composition of the present invention can be prepared by
adding the above mentioned specific alumina particle having a
particle diameter of 10-60 .mu.m and the crystalline
aluminosilicate zeolite to the precursor slurry of a porous
inorganic oxide matrix, for instance such as silica hydrosol,
silica-alumina hydrosol and the like, dispersing uniformly and
spray drying the resulting mixed slurry in a usual manner. The
amounts of the precursor slurry of matrix, the specific alumina
particle and the crystalline aluminosilicate zeolite used are
controlled so that the finally obtained catalyst composition may
contain the specific alumina particle in the range of 5-75 wt. %,
the crystalline aluminosilicate zeolite in the range of 5-50 wt. %
and the matrix in the range of 20-50 wt. % respectively. The spray
dried particles are washed as occasion demands, and then dried
again.
In the catalytic cracking operation of hydrocarbon oils, metallic
contaminants such as vanadium, nickel and the like admixed in the
feed oil deposit on the catalyst to deteriorate the catalytic
activity and gasoline selectivity of the catalyst, and further the
dehydrogenating reaction caused by said deposited metals
conspicuously increases the amounts of coke and hydrogen produced.
In particular, vanadium moves near the crystalline aluminosilicate
zeolite in the catalyst regenerating atmosphere which is normally
maintained at a temperature of 630.degree. C. or more to thereby
destroy its crystal structure.
In the catalytic cracking catalyst composition according to the
present invention, wherein alumina particles having a particle
diameter of 10-60 .mu.m are dispersed as small lumps, metallic
contaminants deposited on the catalyst are caught by said particles
to aggregate thereon, and so do not disperse in the composition.
Accordingly, deposited metals, in particular vanadium, are
prevented from moving near the crystalline aluminosilicate zeolite
even in the catalyst regenerating atmosphere maintained at
630.degree. C. or more, and consequently, destruction of its
crystal structure is also prevented. It is conjectured that the
phosphorus fixed on the alumina particles accelerates aggregation
of metals, such as vanadium, nickel and the like, caught on the
alumina particles, and accelerates deactivation of these metals.
And, when the auxiliary component selected from alkaline earth
metals and rare earth metals is fixed on the alumina particles, it
is conjectured from the test results of the inventors of the
present invention that this auxiliary component possesses very
strong affinity with metal oxides such as vanadium, nickel and the
like. The ability of alumina particles to catch metallic
contaminants deposited on the catalyst is accelerated more and
more. When the auxiliary component of the present invention is
selected from antimony, bismuth, boron, manganese and tin, this
auxiliary component readily forms a solid solution with metals such
as vanadium, nickel and the like, and consequently, markedly
suppresses especially the dehydrating activity of nickel. Further,
this auxiliary component, which is fixed on the alumina particles,
has no possibility of obstructing the catalytic activity.
Thus, the catalyst composition of the present invention, even when
a large amount of metallic contaminants deposit thereon, can
maintain high catalytic activity and high gasoline selectivity, and
can suppress the production of coke and hydrogen to small amounts.
Example 1
An aluminum hydroxide obtained by Bayer's process was calcined at
600.degree. C. in the air for 2 hours. Then, 500 g of this calcined
alumina was weighed. An aqueous phosphoric acid solution (115 ml)
obtained by diluting 82 g of a 85% orthophosphoric acid with water
was added to said calcined alumina and blended for 10 minutes. The
phosphoric acid-added alumina particles were dried at 110.degree.
C. for 17 hours, and thereafter calcined at 600.degree. C. for 1
hour, thereby preparing phosphorus-containing alumina particles.
The average particle diameter of the phosphorus-containing alumina
particles was 30 .mu.m, the phosphorus content thereof was 4.0 wt.
% (0.07 in terms of P/Al atomic ratio), and the specific surface
area thereof was 67 m.sup.2 /g respectively. A mixed slurry was
obtained by adding 500 g of said phospho- rus-containing alumina
particles to 4000 g of the silica hydrosol containing 5 wt. % of
SiO.sub.2 prepared by adding sulfuric acid to water glass, and
further adding 300 g of a hydrogen ion-exchanged Y-type zeolite
thereto. Then, this mixed slurry was spray dried, washed, and
further dried to obtain a catalytic cracking catalyst composition
of the present invention.
This catalyst composition contained 50 wt. % of the
phosphorus-containing alumina particles, 30 wt. % of the H-Y
zeolite and 20 wt. % of the silica derived from the matrix, and had
the average particle diameter of 68 .mu.m. This catalyst
composition is named Catalyst A.
Comparative Example 1
This example relates to the usual catalyst described in U.S. Pat.
No. 4,228,036. An aluminum sulfate solution was neutralized with
ammonia water, and the resulting aluminum hydroxide precipitate was
washed to remove by-product salt. A 85% ortho-phosphoric acid was
added, while stirring, to this alumina hydrogel slurry
corresponding to the amount of 450 g as Al.sub.2 O.sub.3 so that
the phosphorus content of the alumina became 4.0%, thereby
obtaining a phosphorus-containing alumina hydrogel slurry. 6250 g
of said phosphorus-containing alumina hydrogel slurry was added to
4000 g of a silica hydrosol having a SiO.sub.2 concentration of 5
wt. % prepared by adding sulfuric acid to water glass, and further
300 g of H-Y zeolite was added thereto, thereby preparing a mixed
slurry. Then, this slurry was spray dried in the same manner as
Example 1, washed and further dried to thereby obtain a catalytic
cracking catalyst composition.
This catalyst composition contained phosphorus and alumina in the
total amount of 49.8 wt. %, 30.1 wt. % of H-Y zeolite and 20.1 wt.
% of the silica derived from the matrix. This is named Catalyst
B.
Comparative Example 2
This example relates to the usual catalyst corresponding to U.S.
Pat. No. 4,430,199. A commercially available water glass No. 3 was
diluted to thereby prepare a water glass solution having a
SiO.sub.2 concentration of 11.2%. A 10.5% aluminum sulfate solution
was prepared separately. The water glass solution and the aluminum
sulfate solution were mixed while pouring in a vessel in the ratios
of 20 1/min. and 10 1/min. respectively, to thereby prepare a
silica-alumina hydrogel slurry. This slurry was aged at 65.degree.
C. for 3.5 hours, and then a water glass solution was added thereto
for adjusting the pH to 5.8 and stabilized. Thereafter, this slurry
was added to H-Y zeolite so that the zeolite content of the final
catalyst composition might become 30 wt. %. The obtained mixed
slurry was spray dried in the same manner as Example 1, washed and
dried to obtain a phosphorus-free catalyst composition.
Next, this catalyst was calcined at 600.degree. C. for 1 hour, 200
g of this calcined catalyst was impregnated with 60 g of a 22%
ortho-phosphoric acid aqueous solution having the pH of 3.5
adjusted with ammonia water, and thereafter dried to thereby obtain
a phosphorus-containing catalyst composition.
TABLE 1 ______________________________________ Evaluation of metals
tolerance Catalyst A B C ______________________________________
Deposited metal amount Ni ppm 0 4000 0 4000 0 4000 V ppm 0 4000 0
4000 0 4000 Activity evaluation Conversion wt % 59.8 45.1 67.5 39.0
57.2 20 C.sub.5.sup. + 45.7oline wt % 32.1 47.1 26.5 43.8 <15
Coke wt % 1.2 2.4 2.4 2.4 1.0 -- Hydrogen wt % 0.04 0.37 0.06 0.39
0.04 -- ______________________________________
This catalyst contained 2.0 wt. % of phosphorus, 28.6 wt. % of H-Y
zeolite, and 66.8 wt. % of silica-alumina. This catalyst is named
Catalyst C.
Example 2 (Evaluation of catalytic performance)
The above mentioned Catalysts A-C were each subjected to
performance evaluation using ASTM MAT.
First, for the purpose of investigating the metals tolerance of
each catalyst, nickel and vanadium were deposited on each catalyst
in the following manner.
This is, each catalyst had previously been calcined at 600.degree.
C. for 1 hour, was allowed to absorb a predetermined amount of
benzene solution of nickel naphthenate and vanadium naphthenate,
then dried at 110.degree. C. and thereafter calcined at 600.degree.
C. for 1.5 hours. Therafter, each catalyst was steam deactivated by
treating with 100% steam at 770.degree. C. for 6 hours and
calcining again at 600.degree. C. for 1 hour. Each catalyst, on
which nickel and vanadium had not been deposited, was treated with
100% steam at 770.degree. C. for 6 hours, and calcined at
600.degree. C. for 1 hour. The thus pretreated catalyst was
subjected to evaluation tests using ASTM MAT. The obtained results
are shown in Table-1.
The reaction conditions used herein are as shown below.
Feed oil: desulfurized vacuum gas oil
Reaction temperature: 482.degree. C.
Space velocity: 16 hr-1
Catalyst/oil ratio: 3 (by weight)
TABLE 1 ______________________________________ Evaluation of metals
tolerance Catalyst A B C ______________________________________
Deposited metal amount Ni ppm 0 4000 0 4000 0 4000 V ppm 0 4000 0
4000 0 4000 Activity evaluation Conversion wt % 59.8 45.1 67.5 39.0
57.2 20 C.sub.5.sup. + 45.7oline wt % 32.1 47.1 26.5 43.8 <15
Coke wt % 1.2 2.4 2.4 2.4 1.0 -- Hydrogen wt % 0.04 0.37 0.06 0.39
0.04 -- ______________________________________
As shown in Table-1, Catalyst A corresponding to the catalyst
composition of the present invention can maintain high cracking
activity and high gasoline selectivity even when large amounts of
metals have deposited thereon, and further, can suppress the
production rate of coke an hydrogen to a low level in spite of its
high cracking activity. In contrast with this, Catalyst B of
Comparative Example 1 and Catalyst C of Comparative Example 2 are
markedly inferior in the cracking activity and gasoline selectivity
because of the deposition of large amounts of metals.
Next, metal-deposited Catalyst A and Catalyst B were investigated
about the distribution of Al, Si and V in the catalyst particle
using XMA. This measurement was made according to the method
described in J. Japan Petrol. Inst., vol. 26, page 344 (1983). The
obtained results are shown in FIG. 1 (Catalyst A) and FIG. 2
(Catalyst B).
As is evident from comparison of FIG. 1 with FIG. 2, in the case of
Catalyst A, in which alumina was dispersed in the particle form, Al
and V show substantially the same distribution, and this phenomenon
establishes that V has selectively deposited on alumina. In the
case of Catalyst B, whilst, it can be seen that V has uniformly
deposited in the catalyst particle.
Example 3
The aluminum hydroxide (average particle diameter: 50 um) obtained
by Bayer's process was treated with phosphoric acid in the same
manner as Example 1 to thereby prepare phosphorus-containing
alumina particles having the phosphorus contents of 0.008, 0.14 and
0.22 in terms of P/Al atomic ratio. These phosphorus-containing
alumina particles were treated according to the same procedure as
Example 1 to obtain Catalysts D, E and F containing 50 wt. % of the
phosphorus-containing alumina particle, 30 wt. % of the H-Y zeolite
and 20 wt. % of silica.
Next, predetermined amounts of nickel and vanadium were deposited
on each of these catalysts according to the same method as Example
2. The metal-tolerance of each catalyst was evaluated under the
same conditions as Example 2. The results are shown in Table-2.
Catalyst D and Catalyst F, in which the P/Al atomic ratio of the
phosphorus-containing alumina deviates from the range of 0.01-0.20,
are inferior in gasoline yield and form more coke as compared with
Catalyst E.
TABLE 2 ______________________________________ Evaluation of metals
tolerance Catalyst D E F ______________________________________
P/Al atomic ratio of phosphorus- 0.008 0.14 0.22 containing alumina
Deposited metal amount Ni ppm 3000 3000 3000 V ppm 3000 3000 3000
Activity evaluation Conversion wt % 47.5 47.9 41.1 C.sub.5.sup. +
gasoline wt % 33.6 35.2 30.6 Coke wt % 3.0 2.6 2.8 Hydrogen wt %
0.42 0.37 0.38 ______________________________________
Example 4
An aqueous solution of RECl.sub.3 corresponding to 2.1 wt. % as
rare earth metal (RE) was added to the phosphorus-containing
alumina particle (phosphorus content 4.0 wt. %, average particle
diameter 30 .mu.m) prepared in Example 1 and mixed, then dried at
110.degree. C. for 17 hours and further calcined at 600.degree. C.
for 2 hours, hereby preparing an alumina particle on which the RE
and phosphorus had fixed.
500 g of said RE-fixed phosphorus-containing alumina particle was
added to 4000 g of a 5 wt. % SiO.sub.2 -containing silica hydrosol
prepared by adding phosphoric acid to a water glass, and further
300 g of hydrogen ion-exchanged Y-type zeolite was added thereto to
thereby prepare a mixed slurry. Then, this mixed slurry was spray
dried, washed and further dried to obtain a catalytic cracking
catalyst composition according to the present invention.
This catalyst composition contained 50 wt. % of the RE and
phosphorus-fixed alumina particle, 30 wt. % of the H-Y zeolite, and
20 wt. % of silica derived from the matrix. This catalyst
composition is named G.
Example 5
A catalyst composition was prepared according to the same manner as
Example 4 except that an aqueous Mg (N.sub.3)2 solution was used in
place of the aqueous RECl.sub.3 solution This catalyst composition
contained 4.8 wt. % of P.sub.2 O.sub.5, 1.2 wt. % of MgO and 44 wt.
% of Al.sub.2 O.sub.3. This catalyst is named Catalyst H.
Example 6
An aluminum hydroxide (average particle diameter
50 .mu.m) obtained by Bayer's process was treated with phosphoric
acid according to the same manner as Example 1 to thereby obtain a
phosphorus-containing alumina particle, the phosphorus content of
which was 8.5 wt. % (0.17 in terms of P/Al atomic ratio) of
alumina. This phosphorus-containing alumina particle was added to
an aqueous CaCl.sub.2 solution corresponding to 2.1 wt. % as Ca,
and processed in the same manner as Example 4 except that the
aqueous RECl.sub.3 solution was not employed, thereby obtaining a
catalyst composition. This is named Catalyst I.
Comparative Example 3
An aluminum sulfate solution was neutralized with ammonia water,
and the resulting aluminum hydroxide precipitate was washed to
remove by-product salt. 78 g of a 85% ortho-phosphoric acid was
added, while stirring, to this alumina hydrogel slurry
corresponding to the amount of 440 g as Al.sub.2 O.sub.3, and then
an aqueous magnesium nitrate solution corresponding to 12.4 g as
MgO was added thereto.
4000 g of a silica hydrosol (SiO.sub.2 concentration 5 wt. %)
prepared by adding sulfuric acid to water glass was added to said
slurry, and further 300 g of H-Y zeolite was added thereto to
thereby prepare a mixed slurry. Then this slurry was spray dried
according to the same manner as Example 1, washed and further dried
to thereby obtain a catalytic cracking catalyst composition.
This catalyst composition contained 4.8 wt. % of P.sub.2 O.sub.5,
1.2 wt. % of MgO and 44 wt. % of Al.sub.2 O.sub.3. This is named
Catalyst J.
Example 7 (Evaluation of catalyst performance)
The above mentioned Catalysts G-J and Catalyst A obtained by
Example 1 were subjected to performance evaluation using ASTM MAT
in the exactly same manner as described in Example 2. The obtained
results are shown in Table-3.
TABLE 3
__________________________________________________________________________
Evaluation of metals tolerance Catalyst G H I A J
__________________________________________________________________________
Deposited metal amount Ni ppm 0 3000 0 3000 0 3000 0 3000 0 3000 V
ppm 0 3000 0 3000 0 3000 0 3000 0 3000 Activity evaluation
Conversion wt % 62.2 54.5 60.5 53.1 62.8 53.5 59.8 48.4 65.7 30.5
C.sub.5.sup. + gasoline wt % 48.1 39.2 46.0 38.2 47.9 38.7 45.7
35.6 47.0 22.0 Coke wt % 1.6 2.7 1.4 2.6 1.5 2.6 1.2 2.6 2.4 2.0
Hydrogen wt % 0.04 0.29 0.04 0.28 0.04 0.31 0.04 0.36 0.05 0.38
__________________________________________________________________________
As shown in Table-3, Catalysts G, H and I, according to the present
invention, are high in the conversion after nickel and vanadium
have deposited, are high in gasoline yield, and form low amounts of
coke and hydrogen, as compared with the catalyst J comprising the
matrix in which MgO, P.sub.2 O.sub.5, Al.sub.2 O.sub.3 and
SiO.sub.2 have uniformly dispersed and the zeolite.
Example 8
An aqueous SbCl.sub.3 solution corresponding to 1.2 wt. % as Sb was
added to the phosphorus-containing alumina particle (phosphorus
content 4.0 wt. %, average particle diameter 30 .mu.m) in Example 1
and stirred, thereafter dried at 110.degree. C. for 17 hours, and
further calcined at 600.degree. C. for 2 hours, thereby preparing
an alumina particle on which antimony and phosphorus had fixed.
500 g of said antimony-fixed phosphorus-containing alumina particle
was added to 4000 g of a 5 wt. % SiO.sub.2 -containing silica
hydrosol prepared by adding sulfuric acid to water glass, and
further adding 300 g of a hydrogen ion-exchanged Y-type zeolite to
prepare a mixed slurry. Then, this mixed slurry was spray dried,
washed and further dried to obtain a catalytic cracking catalyst
composition according to the present invention.
This catalyst composition contained 50 wt. % of the antimony and
phosphorus-fixed alumina particle, 30 wt. % of H-Y zeolite and 20
wt. % of the silica derived from the matrix. This catalyst
composition is named Catalyst K.
Example 9
A catalyst composition was prepared in the same manner as Example 8
except that an aqueous Bi(NO.sub.3)2 solution corresponding to 1.2
wt. % as Bi was used in place of the aqueous SbCl.sub.3 solution.
This catalyst composition contained 4.61 wt. % of P.sub.2 O.sub.5,
0.67 wt. % of Bi.sub.2 O.sub.3 and 44.7 wt. % of Al.sub.2 O.sub.3.
This catalyst composition is named Catalyst L.
Comparative Example 4
An aluminum sulfate solution was neutralized with ammonia water,
and the resulting aluminum hydroxide precipitates were washed to
remove by-product salt. 90 g of a 85% ortho-phosphoric acid was
added while stirring to this alumina hydrogel slurry corresponding
to 490 g as Al.sub.2 O.sub.3. This slurry was added to 4000 g of
silica hydrosol (SiO.sub.2 concentration 5 wt. %) prepared by
adding sulfuric acid to water glass and further added with 300 g of
a H-Y zeolite to thereby prepare a mixed slurry. Then, this slurry
was spray dried in the same manner as Example 1. This spray-dried
composition was dipped in an aqueous SbCl.sub.3 solution
(50.degree. C.) for 10 minutes, thereafter washed with water and
dried to obtain a catalytic cracking catalyst composition.
This catalyst composition contained 4.92 wt. % of P.sub.2 O.sub.5,
0.72 wt. % of Sb.sub.2 O.sub.3 and 43.5 wt. % of Al.sub.2 O.sub.3.
This catalyst composition is named Catalyst M.
Example 10 (Evaluation of catalyst performance)
The above mentioned Catalysts K-M and Catalyst A obtained by
Example 1 were subjected to performance evaluation using ASTM
MAT.
First, for the purpose of investigating the metal tolerance
thereof, nickel alone or both nickel and vanadium were deposited on
samples of each catalyst in the following manner. That is, each
catalyst had previously been calcined at 600.degree. C. for 1 hour,
thereafter was allowed to absorb a predetermined amount of benzene
solution of nickel naphthenate or benzene solution of nickel
naphthenate and vanadium naphthenate, then dried at 110.degree. C.
and thereafter calcined at 600.degree. C. for 1.5 hours.
Thereafter, each catalyst was steam deactivated by treating with
100% steam at 770.degree. C. for 6 hours and calcined again at
600.degree. C. for 1 hour. Samples of each catalyst, on which
nickel and vanadium had not been deposited, were treated with 100%
steam at 770.degree. C. for 6 hours and then calcined at
600.degree. C. for 1 hour.
The thus pretreated catalysts were subjected to evaluation tests
under the same conditions described in Example 2 using ASTM MAT.
The obtained results are shown in Table-4.
TABLE 4
__________________________________________________________________________
Evaluation of metals tolerance Catalyst K L A M
__________________________________________________________________________
Deposited metal amount Ni ppm 0 5000 2000 0 5000 2000 0 5000 2000 0
5000 2000 V ppm 0 0 4000 0 0 4000 0 0 4000 0 0 4000 Activity
evaluation Conversion wt % 59.0 58.3 50.9 59.4 57.1 51.1 59.8 56.6
48.4 61.8 55.8 42.5 C.sub.5.sup. + gasoline wt % 45.1 39.0 37.3
45.5 38.3 36.8 45.7 36.3 35.2 47.6 33.9 30.0 Coke wt % 1.2 2.9 2.5
1.2 3.0 2.6 1.2 4.0 2.9 1.4 3.9 3.1 Hydrogen wt % 0.04 0.21 0.22
0.04 0.23 0.25 0.04 0.40 0.36 0.04 0.37 0.29
__________________________________________________________________________
As shown in Table-4, Catalysts K and L according to the present
invention are high in conversion and gasoline yield after nickel
and vanadium have deposited, and form low amounts of coke and
hydrogen as compared with Catalyst M prepared by impregnating the
antimony compound on catalyst comprising the matrix in which
P.sub.2 O.sub.5, Al.sub.2 O.sub.3 and SiO.sub.2 have been uniformly
mixed. In addition, Catalysts K and L are high in conversion and
gasoline yield as compared with Catalyst A which contains no
auxiliary component.
Example 11
This Example shows the influences exerted by the particle diameters
of alumina particles impregnated with a phosphorus component.
An aluminum hydroxide (average particle diameter: 60 microns)
obtained by Bayer's process was calcined at 600.degree. C. in air
for 2 hours to obtain a calcined alumina (a).
Then, part of said calcined alumina (a) was ground to obtain
alumina particles having an average particle diameter of 3 microns.
500 g of the alumina particles was weighed. An aqueous phosphoric
acid solution (115 ml) obtained by diluting 82 g of a 85%
orthophosphoric acid with water was added to said alumina particles
and blended for 10 minutes. The phosphoric acid-added alumina
particles were dried at 110.degree. C. for 17 hours, and thereafter
calcined at 600.degree. C. for 1 hour, thereby preparing
phosphorus-containing alumina particles. The average particle
diameter of the phosphorus-containing alumina particles was 3
microns, and the phosphorus content thereof was 4.0 wt. % (0.07 in
terms of P/Al atomic ratio).
A mixed slurry was obtained by adding 500 g of the
phosphorus-containing alumina particles to 4000 g of a silica
hydrosol containing 5 wt. % of SiO.sub.2 prepared by adding
sulfuric acid to water glass, and further adding 300 g of a
hydrogen ion-exchanged Y-type crystalline aluminosilicate
(zeolite). Then, this mixed slurry was spray dried, washed and
further dried to obtain a catalytic cracking catalyst composition
of the present invention.
This catalyst composition contained 50 wt. % of the
phosphorus-containing alumina particles, 30 wt. % of the H-Y
zeolite and 20 wt. % of the silica derived from the matrix, and had
an average particle diameter of 62 microns. This catalyst
composition is named Catalyst N.
In accordance to the same procedure ss described above, part of the
calcined alumina (a) was ground to prepare alumina particles having
an average alumina particle diameter of 10 microns, 15 microns and
20 microns respectively. By using said alumina particles
respectively and in accordance to the same procedure as described
above, there were prepared catalyst compositions containing 50 wt.
% of the phosphorus-containing alumina particles, 30 wt. % of the
H-Y zeolite and 20 wt. % of the silica derived from the matrix.
Those catalysts are named 0, P and Q respectively.
The above-mentioned catalysts N-Q were each subjected to
performance evaluation using ASTM MAT.
First, for the purpose of investigating the metal tolerance of each
catalyst, nickel and vanadium were deposited on samples of each
catalyst in the following manner. That is, samples of each catalyst
were previously calcined at 600.degree. C. for 1 hour, and then
were allowed to absorb a predetermined amount of benzene solution
of nickel naphthenate and vanadium naphthenate, then dried at
110.degree. C. and thereafter calcined at 600.degree. C. for 1.5
hours. Thereafter, each catalyst was deactivated by treating with
100% steam at 770.degree. C. for 6 hours, and calcined at
600.degree. C. for 1 hour.
The thus pretreated catalysts were each subjected to evaluation
tests using ASTM MAT. The obtained results are shown in Table 5 and
FIG. 3 together with the results of Catalyst A and Catalyst B.
The reaction conditions used herein are as shown below:
Feed oil : desulfurized vacuum gas oil
Reaction temperature: 482.degree. C.
Space velocity : 16 hr.sup.-1
Catalyst/oil ratio : 3 (by weight)
TABLE 5
__________________________________________________________________________
Evaluation of Metals Tolerance Catalyst B N O P Q A
__________________________________________________________________________
Diameter of phosphorus- -- 3 10 15 20 30 containing alumina
particle, micron Deposited metal amount Ni ppm 0 4000 0 4000 0 4000
0 4000 0 4000 0 4000 V ppm 0 4000 0 4000 0 4000 0 4000 0 4000 0
4000 Activity evaluation Conversion wt. % 67.5 39.0 61.5 40.5 60.3
41.6 60.6 43.8 60.5 44.5 59.8 45.1 C.sub.5.sup. + 47.1oline wt. %
26.5 45.9 30.1 45.1 30.6 45.7 31.9 45.6 32.1 45.7 32.1 Coke wt. %
2.4 2.4 1.2 2.4 1.2 2.4 1.2 2.4 1.2 2.3 1.2 2.4 Hydrogen wt. % 0.06
0.39 0.04 0.41 0.04 0.39 0.04 0.37 0.04 0.37 0.04 0.37
__________________________________________________________________________
FIG. 3 is a view plotting the conversion of the feed oil, using
nickel and vanadium-deposited catalysts, against the diameters of
phosphorus-containing alumina particles of said catalysts.
As is seen from Table 5 and FIG. 3, the conversion of the feed oil,
using the nickel and vanadium-deposited catalysts increases as the
diameter of phosphorus-containing alumina particles of the
catalysts increases.
Example 12
This Example shows the use of an auxiliary component-incorporated
zeolite in the place of incorporating said auxiliary component in
alumina particles impregnated with a phosphorus component.
An aluminum hydroxide obtained by Bayer's process was calcined at
600.degree. C. in air for 2 hours. Then, 500 g of this calcined
alumina was weighed. An aqueous phosphoric acid-solution (115 ml)
obtained by diluting 82 g of a 85% orthophosphoric acid with water
was added to said calcined alumina and blended for 10 minutes. This
phosphoric acid-added alumina particle was dried at 110.degree. C.
for 17 hours, and thereafter calcined at 600.degree. C. for 1
hours, thereby preparing phosphorus-containing alumina particles.
The average particle diameter of the phosphorus-containing alumina
particles was 30 microns, and the phosphorus content thereof was
4.0 wt. % (0.07 in terms of P/Al atomic ratio).
On the other hand, an ammonium-exchanged Y-type zeolite was
ion-exchanged with an aqueous magnesium chloride solution by a
conventional manner, thereby obtaining Y-type zeolite having an
exchange rate of magnesium of 42.3%.
Then, 4000 g of a silica hydrosol having a SiO.sub.2 concentration
of 5 wt. % prepared by adding sulfuric acid to water glass was
added with 500 g of said phosphorus-containing alumina particle,
and further with 300 g of said magnesium-exchanged Y-type zeolite,
thereby preparing a mixed slurry. Then this mixed slurry was spray
dried, washed and further dried to thereby obtain a catalytic
cracking catalyst composition. This catalyst composition contained
50 wt. % of the phosphorus-containing alumina particle, 30 wt. % of
the magnesium-exchanged Y-type zeolite and 20 wt. % of the silica
derived from the matrix, and the amount of MgO in this catalyst was
1.1 wt. %. This is named Catalyst R.
Catalyst S was prepared by the exactly same procedure as that
employed in the preparation of said Catalyst R excepting the use of
a RE-exchanged Y-type zeolite (exchange rate: 25.6%) whose ion
exchange was conducted by the use of an aqueous rare earth chloride
solution in place of the aqueous magnesium chloride solution. The
RE content in this catalyst was 2.1 wt. % in terms of oxide.
Catalyst R and Catalyst S were subjected to performance evaluation
in the same procedure as used in the aforesaid Example 11.
The obtained results are shown in Table-6 together with the results
of Catalyst G and Catalyst H.
TABLE 6
__________________________________________________________________________
Evaluation of Metals Tolerance Catalyst R S H G
__________________________________________________________________________
Auxiliary component Mg RE Mg RE Deposited metal amount Ni ppm 0
3000 0 3000 0 3000 0 3000 V ppm 0 3000 0 3000 0 3000 0 3000
Activity evaluation Conversion wt. % 65.3 40.8 66.4 45.9 60.5 53.1
62.2 54.5 C.sub.5.sup.+ gasoline wt. % 47.5 33.0 47.9 35.0 49.0
38.2 48.1 39.2 Coke wt. % 1.9 2.0 2.1 2.6 1.4 2.6 1.6 2.7 Hydrogen
wt. % 0.04 0.39 0.04 0.39 0.04 0.28 0.04 0.29
__________________________________________________________________________
Catalyst H and Catalyst G of the present invention which comprise
incorporating such auxiliary components as magnesium and rare earth
components in alumina particles impregnated with a phosphorus
component are observed to exhibit a higher conversion of the feed
oil, using nickel and vanadium-deposited catalysts, then Catalyst R
and Catalyst S that use the zeolites ion-exchanged with such
auxiliary components as magnesium and rare earth components.
* * * * *